Work

Exploiting Imine Photochemistry for Masked N‐Centered Radical Reactivity

Year: 2019

Type: article

Abstract: This report details the development of a masked N‐centered radical strategy that harvests the energy of light to drive the conversion of cyclopropylimines to 1‐aminonorbornanes. This process employs the N‐centered radical character of a photoexcited imine to facilitate the homolytic fragmentation of the cyclopropane ring and the subsequent radical cyclization sequence that forms two new C−C bonds en route to the norbornane core. Achieving bond‐forming reactivity as a function of the N‐centered radical character of an excited state Schiff base is unique, requiring only violet light in this instance. This methodology operates in continuous flow, enhancing the potential to translate beyond the academic sector. The operational simplicity of this photochemical process and the structural novelty of the (hetero)aryl‐fused 1‐aminonorbornane products are anticipated to provide a valuable addition to discovery efforts in pharmaceutical and agrochemical industries.

Source: Angewandte Chemie

DOI: 10.1002/ange.201909492

Authors: Daryl Staveness, James L. Collins, Rory C. McAtee, Corey R. J. Stephenson

Institution: University of Michigan

Language: English

Topic: Radical Photochemical Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: U.S. Department of Health and Human Services, American Cancer Society, National Science Foundation of Sri Lanka, National Institute of General Medical Sciences

Awards: G1430914028, G3385014294, G4403298635, G5162923015